Vat dye and intermediate



Patented July 31 1951 vAT DYE AND INTERMEDIATE Wilhelm Schmidt-Nickels, Little York, N. .L, as-

signor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application February 19, 1949, Serial No. 77,439

6 Claims. (01. 260329.3)

This invention relates to new and valuable vat dyestuffs containing a benzanthrone nucleus and intermediates therefor and particularly to dyestuffs containing a benzanthrone nucleus reacted with a biphenylene sulfide to form a fast bright orange dye.

In the prior art dyestuffs have been prepared by reacting benzanthrone Bz ecarboxylic acid chloride with other compounds. None of these dyestuffs, however, are known to be similar in structure or properties to that which I have discovered.

The dyestuifs of my invention are obtained by reacting benzanthrone-Bzi-carboxylic acid chloride with. biphenylene sulfide followed by a ring closure. The resultin dyestuffs have the following general formula:

said compounds being unsubstituted or containing one or more nuclear substituents of the class consisting ofhalogen, alkyl, alkoxy. and acylamino groups.

The dyestuffs of this invention are prepared by reacting a molar portion of, biphenylene sulfide and two molar portions of benzanthrone BZI- carboxylic acid chloride in presence of anhydrous aluminum chloride in a solvent such as -nitrO- benzene. The resultant compound is then ringclosed as by the use of aluminum chloride and sodium chloride melt in presence ofoxysen. The first reaction is preferably carried out at a temperature in the range 60 to 100 C. and preferably in the range "70 to 80 C. The ring closure may be accomplished at a temperature of about 140 to 170 C. The time of the first reaction is several hours while the aluminum chloride-sodium chloride-oxygen treatment takes only about y 2 one hour. The dyestufis obtained dye cotton and other cellulose fibers a bright orange in the usual vat dye process to shades having excellent fastnose to chlorine bleach.

A preferred method of preparing the dyestufis of my invention is illustrated by the following example, wherein parts are by weight, but it will be understood that the invention is not limited thereto and that variations and substitutions may be made within the scope of the appended claims.

Example A charge of parts nitrobenzene, 4.1 .parts ben zanthrone Bziecarboxylic acid chloride, 13.8 parts anhydrous aluminum chloride, 1.2 parts biphenylene sulfide is stirred at 7 580 C. for 3 hours. The reaction product is poured into a-little water containing 12 parts concentrated hydrochloric acid (35%). The nitrobenzene is then removed bysteam distillation. The solid reaction product is filtered and for removal of possibly present benzanthrone-Bzi-carboxylic acid extracted at C. with a mixture of 36 parts concentrated ammonia (28%) and 200 parts water. The remaining ketone is filtered, washed neutral and dried. The cyclization of the ob tained ketone is carried out as follows:

A charge of parts anhydrous aluminum chloride, 26 parts sodium chloride is heated to C. at which temperature there is added to the melt under agitation 3 parts of the ,ketone.

A fast stream of dry oxygen isblown through the melt under agitation at -160" C. for 1 hour. The reaction product is poured into 400 parts water and 120 parts concentrated hydrochloric acid (35%).

After boiling for 10 minutes the dyestufi" is fil-. tered, washed neutral and dried. A dyestuff paste can be made by the known method of dis:

solving the dyestuff in concentrated sulfuric acid and pouring the solution in water. The product dyes cotton from a violet hydrosulfite vat a bright orange shade of excellent chlorine fastness.

Analysis: Found: C4sH2oO4S: S=4=.79%.

S=5.00%. Theory for This reaction may be represented by the lowing scheme:

a 4 (1)\ c s 1 nitrobenzene Similar dyestuffs are obtained by employing, instead of biphenylene sulfide and benzanthrone Bzi-carboxylic acid chloride in the foregoing example, equivalent quantities of nuclear substitution products of either one or both of these intermediates containing one or more alkyl groups apiece. Alternatively, the compound obtained by the example, unsubstituted or containing allryl substituents may have other substituents introduced by the known procedures such as halogen, alkoxy, and acylamino. Substituent alkyl groups in the original intermediates, of course, may not be present in positions to block the reaction and ring closure (4 in the benzanthrone and 2,3,6}? in the biphenylene sulfide). It will be understood that such groups as halogen groups present in the original intermediates might not withstand the drastic conditions of the reactions and if thesesubstituents are desired,'

they may be introduced after the dyestuff has 7 been formed by procedures customarily used for introducing such substituents into vat dyestuifs of the benzanthrone series.

If desired, bright orange vat dyestuffs of this invention can be converted into the alkali metal salt of the sulphuric acid ester of the corresponding leuco compound by the usual methods, for example, by reduction of the dyestuffs with a hydrogen liberating metal such as iron, preferably s accompanied by a minor amount of copper, in

a mixture of chlorsulfonic acid and pyridine followed by drowning of the reaction mixture in an aqueous alkali metal carbonate solution and salting out of the resulting leuco ester salt after removal of the pyridine by distillation. The rcsulting leuco sulphuric acid ester salts yield shades having color and fastness properties similar to those obtained by vat dyeing processes from the original dyestuffs, upon application by 4 printing or dyeing of the material and development of the color by treatment with an acid oxidizing bath. I claim: 1. A vat dyestuff having the following formula:

0"" l 2. A compound having the following formula:

3. An alkali metal salt of the sulphuric acid ester of the leuco compound of the dyestuff defined in claim 2.

4. A process for preparing a bright orange vat d'yestuff of the benzanthrone series which comprises reacting two mols of benzanthrone-Bzlcarboxylic acid chloride with one mol of biphenylene-sulfide at an elevated temperature and subsequently ring-closing the ketone obtained therefrom. 7 a 5. A new composition of matter selected from the class consisting of a compound having the following formula:

l t and nuclear alkyl, halo, alkoxy and acylamino derivatives thereof.

6. A- new composition of matter selected from the class consisting of a compound having the following formula:

and nuclear alkyl, halo, alkoxy and acylamino derivatives thereof.

WILHELM SCHMIDT-NICKELS.

No references cited.

i i em m \r.r.m c. r e Certificate of Correction Patent No. 2,562,872 July 31, 1951 WILHELM SCHMIDT-NICKELS It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 31, for the claim reference numeral 2 ould be r rm to the record of the ca is 25th day of D read 1;

ead as corrected above, so that se in the Patent Oflice. ecember, A. D. 1951.

[SEAL] THOMAS F. MURPHY, Assistant 00mm zssz'oner of Patents. 

5. A NEW COMPOSITION OF MATTER SELECTED FROM THE CLASS CONSISTING OF A COMPOUND HAVING THE FOLLOWING FORMULA: 